Organoaluminum oxide catalyst composition



United States Patent 3,219,591 ORGANGALUWNUM OXIDE CATALYST CGMPQSETION Edwin J. Vandenherg, Wilmington, DeL, assignor to Hercules Powder Company, Wilmington, Del :1 corporation of Delaware No Drawing. Original application May 11, 1959, Scr. No. 812,079, now Patent No. 3,135,705, dated June 2, 1964. Divided and this application Jan. 16, 1964, Ser. No. 338,008

18 Claims. (Cl. 252- 331) This application is a division of U.S. application Serial No. 812,079, filed May 11, 1959, now US. Patent 3,135,- 705, which application was a continuation-in-part of US. application Serial No. 738,626, filed May 29, 1958, and now abandoned.

This invention relates to a new process of polymerizing epoxides and more particularly to an improved process of polymerizing epoxides with an organoaluminum compound.

In accordance With this invention, it has been discovered that greatly improved results are obtained in the polymerization of epoxides when an organoaluminum compound that has been reacted and/or complexed with water Within a given molar ratio is used as a catalyst for the polymerization. Just what the function of the water may be is not known, but the amount of water that is present in the polymerization mixture is critical and should be an amount within the range of from about 0.1 mole of water to 1 mole of the organoaluminum compound used as catalyst up to about 1.5 moles of water to 1 mole of the organoalurninurn compound. By carrying out the polymerization in accordance with this invention, it has been found that the conversion and/or yield are greatly improved over the process when no water is used and in many cases a much higher molecular weight polymer is also obtained. Frequently, the crystallinity of the polymer is greatly improved and the amount of the crystalline polymer is a greater percentage of the total polymer. By the proper choice of the organoaluminurn compound that is reacted with the water, one may favor the formation of either a crystalline or crystallizable polymer or an amorphous polymer in those cases where both forms of the polymer exist. Many other advantages will be apparent from the following description.

Any epoxide may be homopolymerized or copolymerized with a second epoxide by the process of this invention to obtain improved results. Exemplary of the epoxide that may be homopolymerized or copolyrnerized are the alkylene oxides such as ethylene oxide, propylene oxide, bu'tene oxides, isobutylene epoxide, substituted alkylene oxides such as epicholorohydrin, epibromohydrin, methallyl chloride epoxi-de, trifiuoromethyl ethylene oxide, perfiuoropropylene oxide, perfiuoroethylene oxide, vinyl chloride epoxide, dichloroisobutylene epoxide, 1,2- dichloro-3,4-epoxybutane, l-chloro 3,4 epoxybutane, lchloro-4,S-epoxypentane, l,l-dichl0ro-2,3-epoxypropane, l,1,l-trichloro-2,S-epoxypropane, 1, Ll-trichloroGA-epoxybutane, etc., cycloali-phatic epox-ides such as cyclohexene oxides, vinyl cyclohexene oxides (monoand dioxides), a-pinene epoxide, dipentene epoxide, etc., epoxy others such as alkyl glycidyl others as, for example, methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, n-hexyl glycidyl ether, n-octyl glycidyl ether, etc., phenyl glycidyl ether, chlorophenyl glycidyl ethers, nitro- 3,Zl,59i Patented Nov. 23, 1965 phenyl glycidyl ethers, alkylphenyl glycidyl ethers, chloroalkyl glycidyl ethers, such as chloroethyl glycidyl ether, bromoethyl glycidyl ether, Z-chlorod-methyl ethyl glycidyl ether, unsaturated glycidyl others such as vinylglycidyl ether, allyl glycidyl ether, etc, glyci-dyl esters such as glycidyl acetate, glycidyl propionate, glycidyl pivalate, glycidyl methacrylate, glycidyl acrylate, etc., alkyl glycidates such as methyl glycidate, ethyl glycidate, etc., and other epoxides as, for example, styrene oxide, flt-mfithylstyrene oxide, butadiene monoand dioxides, epoxy stearates, 1-dimethylamino-2,3 -epoxypropane, trimethyl 2,3-epoxypropyl ammonium chloride, etc. As pointed out above, any of these monoand polyepoxides may be homopolymerized or any mixture of two or more may be copolymerized.

Any organoaluminum compound reacted with water may be used as the catalyst for the polymerization of epoxides in accordance with this invention. Exemplary of thee organoaluminum compounds that may be used are trialkylalurninum compounds, tricycloalkylalum-inum compounds, triarylaluminum compounds, dialkylaluminum hydrides, monoaluminumalkyl dihydrides, dialkylaluminum halides, monoalkylaluminum dihalides, dialkylaluminum alkoxides, monoalkylaluminum dialkoxides, and complexes of these compounds as, for example, the alkali metal aluminum tetraalkyls such as lithiumaluminum tetraalkyl, etc. Thus, these compounds may be defined as any aluminum compounds containing an aluminum to carbon bond or having the formula AlRX where R is any alkyl, cycloalkyl, aryl, or alkaryl radical and X may be alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, amyl, hexyl, octyl, decyl, etc., aryl, such as phenyl, tolyl, halophenyl, etc., cycloalkyl such as cyclohexyl etc., hydrogen, halogen such as chlorine, fluorine, or bromine, alkoxy such as methoxy, ethoxy, isopropoxy, butoxy, isohutoxy, tert-butoxy, etc, and the radical such as acetoxy, stearoxy, benzoxy, etc. Another group of these compounds are those formed by reacting an aluminum alkyl with a polyol such as ethylene glycol, propylene glycol, glycerin, pentaerythrit-ol, sorbitol, catechol, resorcinol, etc., in which case the X in the above formula would be -ORG-A1RX, where R" is alltylene, phenylene, etc. In some cases it may be desirable to complex the organoaluminum compound with a complexing agent such as tetrahydrofuran as, for example, triisobutylaluminum complexed with a molar amount of tetrahydrofuran, etc.

Other types of organoaluininum compounds that may be reacted with water and used as the catalyst in accordance with this invention are the alkylaluminum chelates and alkylaluminum enolates such as those formed by reacting a trialkylaluminum or dialkylaluminum hydride such as triethylaluminum, triisobutylalurninum, diisobutylaluminum hydride, etc., with an organic compound that is capable of forming a ring by co-ordination with its unshared electrons and the aluminum atom. Preferably these chelating agents are characterized by two functional groups, one of which is an OH group or SH group, as for example, a hydroxyl, or an enol of a ketone, sulfoxide or sulfone, an OH of a carboxyl group, etc., which OH or SH group interacts with the trialkylaluminum or dialkylaluminum hydride to form H H H carbonyl (C), ester (CO R), carboxyl (COH) O sulfoxide g sulfone 1% nitroso (A I) nitro (1 I=O) ll ll amino (R N), thiocarbonyl (C) thiocarboxylic (-C-SI-I) ll thio esters (OO R) etc., groups. The ring size formed with the aluminum by the chelating agent preferably contains five or six atoms including the aluminum, but rings with four and seven atoms are also operable. The amount of chelating agent reacted with the alkylaluminum compound will generally be within the range of from about 0.01 to about 1.5 moles of chelating agent per mole of aluminum and preferably will be from about 0.1 to about 1 mole per mole of aluminum alkyl. Exemplary of the chelating agents that may be reacted with a trialkylaluminum or dialkylaluminum hydride and the chelate then reacted with water to produce the catalysts of this invention are diketones, such as acetylacetone, triiluoroacetylacetone, acetonylacetone, benzoylacetone, furoylacetone, thenoyltrifiuoroacetone, dibenzoyl methane, 3-methyl 2,4 pentane-dione, 3-benzyl-2,4-pentane-dione, etc., ketoacids, such as acetoacetic acid, ketoesters such as ethyl acetoacetate, ketoaldehydes such as formylacetone, hydroxyketones such as hydroxyethyl methyl ketone, hydroxyacetone, o-hydroxyacetophenone, 2,S-dihydroxy-p-benzoquinone, etc., hydroxyaldehydes such as salicylaldehyde, hydroxy esters such as ethyl glycolate, 2-hydroxyethyl acetate, dicarboxylic acids and their esters such as oxalic acid, malonic acid, etc., monoesters of oxalic acid, monoand diesters of malonic acid, etc., dialdehydes such as malonaldehyde, alk-oxyacids such as ethoxyacetic acid, ketoximes such as 2,3 -butane-dione-monoxime, dialdehyde monooximes such as glyoxal monoxime, hydrox-- amic acids such as N-phenyl benzohydroxamic acid, dioximes such as dimethyl glyoxime, nitro compounds such as 1,3-nitroalcohols, 1,3-nitroketones, Z-nitroacetic acid, nitroso compounds such as 1,2-nitroso-oximes, etc. Chelating agents with two or more chelating functions may also be used, as for example, 2,5-dihydroxy-p-benzoquinone, bis(1,3-diketones) such as (CH CO CHCH(COCH 2 (CH CO) CH(CH CH(COCH where n is 2, 6, or 10, bis(1,2-ketoximes), bis(1,2-dioximes), etc.

Regardless of the organoaluminurn compound that is used, it should be reacted with water as set forth above in a molar ratio of from about 0.1 mole of water per mole of organoaluminum compound up to about 1.5 moles of water per mole of aluminum compound. Slightly higher amounts of Water may be used but at a ratio of about 2 moles of Water to 1 mole of organoaluminum compound, there is little or no improvement over the use of no water in the polymerization system and when the ratio of water to organoaluminum compound gets appreciably above 2: 1, it has an adverse effect and the polymerization is retarded or otherwise adversely affected. Preferably the molar ratio of water to organoaluminum compound will be in the range of from about 0.211 to about 1:1. The exact amount of water will depend to some extent on the organoaluminum compound, the epoxide being polymerized, the diluent, temperature, etc.

Any desired procedure may be used for reacting the organoaluminum compound with the specified molar ratio of water. Generally better results are obtained if the organoaluminum compound and water are prereacted and the reaction product then added to the polymerization mixture. This may readily be done, and preferably is done, by adding the specified amount of water gradually to a solution of the organoaluminum compound in an inert diluent as, for example, a hydrocarbon diluent such as n-hexane, toluene, or an other such as diethyl ether or a mixture of such diluents. It may also be done in the absence of a diluent. If a chelating agent is used, it may be added before or after reacting with water. The chelating agent and prereacted organoaluminumwater product may also be reacted in situ. These organoaluminum-water reaction products may be used immediately or aged or, if desired, heat-treated in some cases. Excellent results may also be obtained by reacting the organoaluminum compound with the water within the specified molar ratio in situ. This may be accomplished by adding the specified amount of water to the epoxide or mixture of epoxides being polymerized and then adding the organoaluminum compound, or the two may be added to the polymerization reaction mixture simultaneously. If desired, the organoaluminum-water reaction product may be used in combination with other organoaluminum compounds.

The exact nature of this reaction product of the organoaluminum com-pound with the above-specified amount of water is not known. As pointed out, the amount of water reacted with the organoaluminum compound is critical to produce the superior catalyst for the polymerization of epoxides in accordance with this invention. It is believed that a reaction rather than a complex formation takes place. Thus when a trialkylaluminum compound is reacted with water, it has been found that a very rapid and complete reaction occurs to liberate 2 moles of alkane per mole of water. Thus, with triethylaluminum, 2 moles of ethane per mole of water are liberated. The products are believed to be organoaluminum oxide type of compounds, as, for example,

etc. These com-pounds are probably somewhat associated in organic media. The most active or preferred catalyst species is probably the polymeric species where there is about one R group per A1. Regardless of what the theory may be, the reaction product obtained when an organoaluminum compound is reacted with from about 0.1 mole to about 1.5 moles of water per mole of aluminum compound is an outstanding catalyst for the polymerization of epoxides.

Any amount of the organoaluminum-water reaction product may be used to catalyze the polymerization process in accordance with this invention from a minor catalytic amount up to a large excess but, in general, will be within the range of from about 0.2 to 10 mole percent based on the monomer being polymerized and preferably will be within the range of from about 1 to about 5 mole percent based on the monomer being polymerized. The amount used depends in part on such factors as monomer purity, diluent purity, etc., less pure epoxides and diluents requiring more catalyst to destroy reactive impurities. In order to decrease catalyst consumption, it is generally preferred that impurities such as carbon dioxide, oxygen, aldehydes, alcohols, etc., be kept at as low a level as practical.

The polymerization reaction may be carried out by any desired means, either as a batch or continuous process with the catalyst added all at one time or in increments during the polymerization or continuously throughout the polymerization. If desired, the monomer may be added gradually to the polymerization system. It may be carried out as a bulk polymerization process, in some cases at the boiling point of the monomer (reduced to a convenient level by adjusting the pressure) so as to remove the heat of reaction. However, for ease of operanone to 125 C. to total solution and then cooling to 50 C. at which temperature the determination is made, or the RSV for the poly(epichlorohydrins) is determined on a 0.1% solution of the polymer in u-chloronaphthalene tion, it is more generally carried out in the presence of 5 dissolved at 100 C. and the viscosity determined at that an inert diluent. Any diluent that is inert under the temperature. The latter method is more accurate. For polymerization reaction conditions may be used as, for convenience in comparing the data in the following exeflzlample, efthers suchI asdthial ti'lialgyl, gryl or1 cyclloallyl almnlesfll of thehRSVs obgilnsdlpn thg poly(epichlgroe ers as, or examp e, 1et y et er, lpropy et er, 1- y rins 1n eye 0 eXanone ave een converte to i-sopropyl ether, aromatic hydrocarbons such as benzene, the value it would be in a-chloronaphthalene (CN) using toluene, etc., or saturated aliphatic hydrocarbons and the following equation to relate them: iii???afiii iiiiiiifei fiiaii7.11221???i533?! ample, chlonobenzene or haloalkanes such as methyl chlo- In the F6156 Of t other p y diluent a C011- r-ide, methylene chloride, chloroform, carbon tetrachlocentrahon at WhlCh the RSV 1s determined are stipulated. ride;i gtlliylertle dlChltglidB, eitc. Dbviously, any mixturef of EXAMPLES 1 o 3 suc 1uen s may e use an in many cases is pre erable. For example, when saturated aliphatic hydrocargf f gm hdemonstrate Polymerization of bons are used as the diluent, 1t 1s preferable, particularly eplcd P Y rm f an f- ,ummum compounfi g or If a resuscitate assassi ate itte iuent is resent to use t em in a mixture wit i ethers. A comglexing agent for the organo l i erization vessels free of air were charged under nitrogen compound, such as aha. tetrahydl-ofumn, etc, may be with the diluent, diethyl ether and/or n-heptane, and 10 used and is particularly desirable in a bulk polymerization i g g p i g f f f li l f l a .in -xampe ,asouiono ecaays was process. The polymerization process in accordance with this f catzllhist Solution E prepflred by dlhmng invention may be carried out over a wide temperature i i g an P range and ressure. Usuall it will be carried out at a 6p an O mo ar W1 6 a m an tempera: from about e c. up to about 6 c amount equal to a specified molar ratio of water to alkylpreferably from about O to about C. and aluminum compound was then added and the solution more preferably within the range of about to agitated at 30 C. for 16 to 20 hours. In the control, no about 100 C. Usually, the polymerization process will g Y fl catalyst solufiona Exampli 8 he carried out at auto enous ressure, but su eratmos- 6 my aummum was compexe with a me at pheric pressures up to aseveralphundred pound? may be amount of tetrahydrofuran and then tested with and withused if desired and in the same way, subatmospheric pres- 2 5 3; i g' g g f 23 33 sures ma also be used. m Xampe e The f llowing examples exemplify the improved repolymenzanon was Stopped by adding 4 parts of army Suns that may be Obtained on polynwrizino enoxides in drous ethanol. The mixture was then diluted with about accordance with this invention All parts a percenb 40 parts of diethyl ether, after which the ether-insoluble ages are by weight unless otherwise indicated. As will be 40 polylller g fi washeq twlce with ether see; from thesg:1 examples, the process of this invention 31 z ggg g3 ;ggi igfii fiig giggg f ma es it ossi e to not on obtain reatl o d yields of 01y m at but make; it possibgle 35; i again collected, Washed With methanol until neutral, then proper Conditions to prepare a polymer of any desired with a 0.4% solution of Santonox, i.e., 4,4'-thiobis(6-tertmolecular weight. The molecular weight of the poly- 4D figg g g g gi g g g finally was (mad for 16 mers reduced in these xa l sh r ducedpspecific Viscosity g s w In Table I are set forth the total amount of diluent tsrm Reduced Specific Viscosity is meant the um/Q (mixture of n-heptane and diethyl ether) and the percent on a of a f s i gz i 622 zggi g g fig gggz g was reacted with the specified amount of water), the j I total conversion to polymer, the percent conversion to i g l g z g g 6 b annoxldant ether-insoluble polymer and the RSV of the latter and W 1S( f my P 31101) Whlch percent of ether-insoluble polymer present in the total tron 15 prepared y heatmg the polymer and cyclohexa polymen Table I Diluent r Ex. N0. Catalyst Parts Total Ester lnsffluble Polymer percent H Tot 1 Fe ce t Parts Eire; 53??? RSV 5 g (CzHshAl gig 12 an 3.9 07

. s9 .1 17. 6 91 0. 2s 11 5.2 i 2 1 6 96 0. 2s 47 37. 7 3. 5 1 .6 88 0. 57 a3 0.9 3.5 2.7 1 g (l gfHflcfllxlHnfiflfloag. s3 77.9 3.1 04

I. d 2 5 2 a M 17.6 84 camels-116E120 0.51 i7 i l 17.6 88 (CQHQQAICI 0. 48 22 0.2 00 17.6 84 (Gamma-0.51120. 0. 4s 31 10.5 2.2 34' 17.6 89 (ciHiltalom-cirn) 0. 63 3 0.9 2.3 30 17.6 89 (C-gfioiaiotmoino- 5H20 0.63 6 2.9 2.7 is 17.6 (CQHSl2A1OQ-C3H7) 0. 58 a 2 1.9 67 17.6 90 (CzHsMAlO(1C H )-0.5H O 0.58 30 22 2.3i 73 17.6 84 u-cinoaar'rnr 1.08 19 6.3 4.9? as 17.6 84 (l-C4Hg)aA1 THF*-O.7H2O 1.08 87 77 3.6 1 s0 THF tetrahydroturan.

The ether-insoluble polymer produced in Example 8 was extracted with acetone at room temperature for about 16 hours. The cold acetone-insoluble polymer was isolated, washed with acetone and then with acetone containing 0.05% Santonox in acetone and dried. This poly(epichlorohydrin) was highly crystalline by X-ray and had an RSV of 3.9. Films of this polymer were prepared by compression molding the polymer flake at 280 F. (500 p.s.i.) between chrome-plated brass plates. After cooling to room temperature, the films were allowed to crystallize for 0.2-0.5 hours before removing from the press. The films were oriented by cold-drawing 200% at room temperature and set at 70 C. in air. The physical properties of these films before and after orientation are tabulated below.

Unoriented Oriented Tensile strength, p.s.i 2, 800 14, 000 Ultimate elongation, percent 210 37 Tensile modulus, p.s.i 46, 000 70,000

Strain rate of 500% per minute.

Epichlorohydrin was polymerized using the general procedure described for Examples 1 to 8. In Examples 9 and 10, the molar ratios of Water to triethylaluminum or triisobutylaluminum respectively were varied. The catalyst in Examples 10 and 13 was added in four equal portions 0.5 hour apart. In Example 13 the ratio of catalyst to epichlorohydrin was varied. In Examples 11 and 12, the molar ratio of water to aluminum compound was varied but in these cases the water and aluminum compound were reacted in situ by adding the specified amount of water to the epichlorohydrin before injecting the solution of alkylaluminum compound. In each case the polymerization was run for 19 hours at 30 C. The data for each example are set forth in Table II. The amount of catalyst shown in the table is parts of alkylaluminum 4 8 EXAMPLE 14 Amorphous or largely amorphous poly(epichlorohydrin)s prepared, as for example, described in the foregoing examples, and having an RSV of 0.5 and above, i.e. a weight average molecular weight of about 130,000 and above, are elastomeric and are outstanding in that they may be vulcanized to produce highly solvent-resistant vulcanized rubbers. Thus, Example 10b was repeated except that the catalyst solution was added all at one time instead of in four portions at intervals. A total conversion of 100% was obtained, 77% of which was an etherinsoluble polymer. This ether-insoluble polymer contained 13% crystalline polymer, the remainder being amorphous. The polymer after cold milling had an RSV of 0.75.

It was cross-linked by mixing together on a two-roll mill (rolls cooled to about F.) 100 parts of the polymer, 12.5 parts of carbon black, 12.5 parts of neutral silica and 3 parts of hexamethylenediamine carbamate and then heating at 300 F. for 40 minutes. The vulcanizate so obtained had a tensile strength of 1655 p.s.i., a 100, 200, 300 and 400% modulus of 395, 555, 930 and 1510 p.s.i., respectively, an ultimate elongation of 420%, break set of 10%, Shore hardness (A) of 63, and tear strength of 121 lb./in. This vulcanizate of poly(epichlorohydrin) was found to be very stable to outdoor exposure, being unchanged after 3 months exposure. It was also very stable to accelerated aging tests, with no failure in either the Fade-Ometer or Weather-Ometer at 2500 hours exposure.

EXAMPLES 15 TO 26 These examples demonstrate the polymerization of epichlorohydrin with various diluents and organoaluminum compounds. The general procedure described for Examples 1 to 8 was used, the polymerization being run for 19 hours at 30 0, except for Examples 24 to 26 which were run at C. The catalyst used in Example 17 was formed in situ as described above for Examples 11 and 12. In Example 21, the catalyst solution was added in two portions one hour apart and in Example 22 in four equal portions 30 minutes apart. In Example 24, the alkylaluminum compound used was diethylaluminum acetylacetonate formed by reacting triethylaluminum in 60:40 n-heptanezdiethyl ether with acetylacetone in an amount 45 compound pIlOI' to reac -Ion Wlth e equal to one mole per mole of triethylaluminum and agi- Table II Diluent Ether-Insoluble Polymer Ex. Total No. Catalyst Parts Percent Total Percent Conv. Percent Percent of Parts Ether Conv. RSV Total 35 94 (021133111 0. 40 12 8.0 3. 9 e7 35 94 (o2H5 3A1 0.1117o 0. 40 37 32. 3 3. 0 s3 35 94 (O2H Al-0.3HzO 0. 40 32 59. 7 3. 0 91 35 94 (cans) :Al0511z0- 0. 40 82 77. 7 3. 2 95 35 94 (C H5)aAl-0.7H7O o. 40 s9 s5. 9 3. 3 9e 35 94 (anew-1.01120. 0. 40 37 37. 0 1. 9 99 17. 0 s4 (1-C4H9)3A1-O 31120 0. 79 s9 s7 2. 3 9s 17. 6 s4 (l-O4H9)3A1-0 51120.- 0. 79 91 90 1. 7 99 17. 0 s4 (l-C4H9)3A1-0 712120-.-- 0. 79 93 91 1. 7 93 17.0 34 (i-CrHsOaAl-OBH; 0. 79 92 89 2.5 97 35 97 (07am 1 0.23 10 7.5 4.1 35 97 {9am-- 33 55 53 96 35 97 139 5 10 3.5 1.8 35

OH AL- 0.23 35 97 {9.3.7. 0.1. 2 None 0 12a 17.0 33 (l-C4H9)3Al 0. 79 40 5.2 3.0 13 12b 17.6 33 gg gfgf 8 g 04 39 2.9 01

(L011 0.79 120 17.3 83 121 g 73 53 2.5 77 12d 17.0 33 f fffffff I 8:6 s0 03 2.2 79 129------ 17.9 33 5 2? 8:52 23 16 2.3 70 12: 17.6 33 E ?f 8: 0 13a 23 88 (1-C4H9)aAl-05H2O 0.79 93 89 1.1 99 13b 23 88 (i-C4H Al-0.5H2O 0.53 37 1.5 97 13c 23 88 90.111931119315120 0. 20 00 57 1.9

tating for hours at 30 C. In Examples and 26 the alkylaluminum compound used was triisobutylaluminum chelated with 0.5 mole of diethyl malonate and 0.5 mole of N-phenylbenzohydroxamic acid, respectively and agitated at C. for 20 hours. The data for each example are tabulated in Table III. The amount of catalyst added in each case is indicated as the parts of the trialkylaluminurn that was reacted with water in the indicated mole ratio.

The ether-insoluble polymer produced in Example 21 was recrystallized by dissolving in acetone at 65 C. and then allowing it to crystallize at 2030 C. for about 16 hours after which it was collected, washed with acetone containing 0.5% Santonox and dried. The poly(epichlorohydrin) so obtained had an RSV of 2.3 and was shown to be highly crystalline by X-ray. Films of this polymer were prepared as described in Example 8. This film had a tensile strength of 2720 p.s.i., ultimate elongation of 60%, tensile modulus of 86,000 p.s.i. and a tensile impact of 1.20.

In Example 33, the ether-soluble fraction was also soluble in methanol and was precipitated from the methanol by the addition of 20% water. It was a very tacky rubber with an RSV of 0.86 measured as 0.1% solution in cyclohexanone at 50 C. That polymerization had taken place through the oxide linkage and not the ethylene double bond was shown by near infrared, the polymer containing 33.2% allyl (theory 36.0%). This poly(allyl glycidyl ether) was vulcanized by milling 100 parts of the polymer with 50 parts of carbon black, 2 parts of sulfur, and 1.5 parts of mencaptobenzothiazole for 10 minutes and then press curing at 300 F. for minutes. The vulcanizate so obtained was pliant and rubbery. It had a tensile strength of 500 p.s.i., a modulus (100%) of 400 .p.s.i., an ultimate elongation of 120%, a Shore hardness (A) of and a break set of 5%.

The ether-insoluble poly(epibromohydrin) of Exam pic 34 was fractionated by agitating 6.5 parts of it with 200 parts of acetone overnight at room temperature. The acetone-insoluble polymer was separated by filtration,

Table III Diluent Ether-Insoluble Polymer Total Ex. Catalyst Parts Percent No. Total Conv. Percent Percent Parts Components Couv. RSV 0 Total 10 99.1% n-hcptane, 0.0% ether (C2H )3Al-O.6HzO 0.46 76 32 0.07 43 19 85% n-heptane, 15% ether... (CQEI hAl-QGH QN 0.46 84 71 1.3 84 1?. s 100% n-heptane I gg? 60 52 0.14 7 17. 6 11% n-heptane, 89% (liisopropyl other." (C2H3)3Al- .o 0. 16 78 69 2. 2 88 25 83%h CHzClz, 8.5% n-heptane, 8.5% (i-CiHa)aAl-0.5HzO 0. 79 91 90 2. 4 09 et er. 19 79751 C H5Cl, 10.5% n-heptaue, 10.5% (l-CfllghAl-Ojlizh) 0. 79 86 78 0.8 91

e ier.

2. 3 36% n-heptane, 64% ether (CgH5) Al-0.5HQO 0. 19 03 2. 0 7 17. 6 5% n-heptane, 95% ether (nCSH MALOIHZOU H. 1. 54 88 88 2. 9 100 35 27% reheptane, 73% ether (C HQ Al-QSHQO c 1.03 24 10 2. 2 42 17. 6 12% n-heptane, 88% other: (C1115)zAlAcetylaeetonate-0.51120 0. 74 78 76 7. 7 Q8 20 90% n-heptane, 10% ether (l-C4l'Ig)3Al-0.5dletllyll11E1lOl12Lte-0.5II20 0.79 40 36 1.4 90 26 90% n-heptaue, 10% ether; (i-C4Hg) Al 0.5 N-phenylbeuzohydrox- 0. 7 41 35 3. 1 85 male acid-0.51120.

EXAMPLES 27 TO 35 In each of these examples 10 parts of the specified epoxide were polymerized by the general procedure described for Examples 1 to 8 using as the catalyst the reaction product of 0.46 part of triethylaluminum and with 0.04 part of water (molar ratio of 1:0.6), except in the case of Examples 34 and 35 where 0.79 part of triisobutylaluminum was reacted with 004 part of water (molar ratio of 120.5) was used, the total amount of n-heptaneether diluent being 17.6 parts of which 8390% was ether. Each of the polymerizations was carried out for 19 hours at 30 C., except for Example 35 which was run 43 hours. The monomer used and the results obtained in each case are tabulated in Table IV.

In Examples 27-30 the ether-insoluble polymer was separated and purified as described in those examples and in each case was shown to be crystalline by its X-ray diffraction pattern. in Examples 31 and 35 where only an ether'tsoluble polymer was formed, the polymer was isolated from the ether by concentrating the solution and precipitation with about 10 volumes of methanol containing 0.2% Santonox. The polymer so obtained was washed with methanol and dried. The ether-insoluble and ether-soluble polymers in Examples 32 and 33 were recovered in the same way, but the ether-insoluble polymer was washed with ether and then with ether containing 0.2% Santonox and dried.

Washed with acetone and then suspended in sufficient acetone ot make a 1% suspension, and heated to 82 C. in a closed vessel under nitrogen whereby it was dissolved in 4 hours. It was then cooled to 30 C. and allowed to crystallize overnight. The recrystallized acetone-insoluble polymer was again washed with acetone, then with methanol containing 0.2% Santonox and finally was dried for 16 hours at 80 C. There was obtained 1.3 parts of a white, film-like, somewhat rubbery solid. It had an RSV of 1.8 and was shown to be moderately crystalline by X-ray. Analysis for bromine showed agreement with the theoretical value. The acetone-soluble polymer was recovered by combining the acetone extracts and washes, removing the acetone and then treating the residue with 80 parts of methanol containing 0.2% Santonox after which the polymer was dried for 16 hours at 80 C. under vacuum. There was recovered 2.8 parts of the acetone-soluble polymer which was a tough, rubbery material having an RSV of 0.8 and shown to be amorphous by X-ray. Its bromine analysis agreed with the theoretical.

This amorphous poly(ep.ibromohydrin) was crosslinked by milling parts of the polymer with 4 parts of hexamethylenediamine carbamate and then heating for 40 minutes at 300 C. The vulcanizate was quantitatively insoluble in cyclohexanone after 4 hours at 60 C. and had the properties typical of a cross-linked elastomer.

Table IV Ether-Insoluble Polymer Ether-Soluble Polymer Ex. Total No. Monomer percent Conv. Percent RSV M. Pt., Remarks Percent Description Conv. C. Conv.

27- o-Ctllillorophenyl glycidyl 81 1. 0 1 0. 28 162 Crystalline 80 Waxy.

e er. 28-.. p-(gillorophenyl glycidyl 98 3. 7 1 0.50 165 .do 84 Viscous gel.

e er. 29 Butadiene monoxide 24 1. 7 Highly crystalline 19 Soft, waxy solid. 30 Styrene oxide 60 0.9 do Grease. 31.-. Hexyl glycidyl ether 16 None 1. 6 Tacky rubber, RSV 0.69. 32- Z-chloroethyl glycidyl ether- 29 5. 3 Tacky rubbery film 2. 1 veryov iscous liquid, RSV

0. 33- Allyl glycidyl ether 74 0. 06 47 Veryfitaeky rubber, RSV

0.8 84 Epibromohydrin 53 33 3 1. 2 Rubbery 35- Methallyl chloride epoxide. 29 4 0. 24 White powder, highly crystalline, M. Pt. 105 C.

1 0.1% in u-chloronaphthalene at 135 C.

2 0.1% in chloroform at 25 C.

3 0.1% in cyelohexanone at 50 C.

4 Ether-soluble, methanol-insoluble fraction.

EXAMPLE 36 Phenyl glycidyl ether was polymerized using the process described for Examples 27-30, the polymerization being carried out for 19 hours at C. A total conversion of 93% was obtained. The ether-insoluble polymer was highly crystalline and amounted to 84% and had an RSV of 1.7 (0.1% solution in a-chloronaphthalene at 135 C.). The ether-soluble polymer amounted to 9% and was soft and waxy.

The ether-insoluble -poly(phenyl glycidyl ether) was extracted with benzene at room temperature and found to be 94% insoluble therein. Films of this benzene-insoluble polymer were prepared by compression molding the polymer flake between chrome-plated steel platens for 5 minutes at 350 F. and 400 p.s.i., cooling to room temperature and removing the films.

The benzene-insoluble polymer that remained from the above extraction was recrystallized by dissolving it in boiling xylene and then cooling to 30 C. About 70% of it was thereby recrystallized from xylene. This cold xylene-insoluble fraction was highly crystalline by X-ray and had an RSV of 1.8 and a melting point of 201 C. The cold xylene-soluble fraction was rubbery. Films of the xylene recrystallized poly(phenyl glycidyl ether), i.e., the cold xylene-insoluble polymer, were prepared in the same manner as those of the benzene-insoluble fraction. The physical data on each are tabulated below before and after orientation (drawn at 60 C. in a water bath to the indicated percent).

135 C.) and a melting point of 176 C. Analysis for chlorine showed that the copolymer contained 4% epichlorohydrin.

Films of this phenyl glycidyl ether-epichlorohydrin were prepared by compression molding as described in Example 36. The film so obtained had a tensile strength of 1700 psi, ultimate elongation of 320%, and a tensile modulus of 30,000 psi. The film was clear, more flexible than that of poly(phenyl glycidyl ether) being flexible down to at least 20 C., and was capable of being oriented by colddrawing. After orientation by cold-drawing 300% at room temperature, the film had a tensile strength of 11,000 p.s.i., ultimate elongation of 76, and a tensile modulus of 30,000 p.s.i. Exposure of the film in a Fade- Ometer showed it to have good light stability.

EXAMPLE 3 8 To a polymerization vessel with a nitrogen atmosphere was charged 9.8 parts of epichlorohydrin and 0.2 parts of allyl glycidyl ether. These epoxides were copolymerized using the general procedure described for Examples 1-8, the total n-heptane-ether diluent amounting to 35 parts and containing 88% ether. The catalyst used was 0.79 part of triisobutylaluminum which had been prereacted with 0.04 part of water, the latter being added stepwise to the alkylaluminum (0.5 mole of water per mole of aluminum), this catalyst being added to the polymerization reaction mixture in eight portions 15 minutes apart. After 2 hours at 30 C., the total conversion to polymer was Benzene-Insoluble Xylene-Recrystallized olymer Polymer Property Unoriented Oriented Unoriented Oriented RSV 1. 5 1. 8 M Pt, C 201 201 Tensile Strength, p.s.i 2, 500 8,000 2, 900 7, 000 Ultimate Elongation, Percent 210 57 90 40 Tensile Modulus, p.s.i 61, 000 100, 000 00, 000 98, 000 Density 1. 18

EXAMPLE 37 31%. The ether-insoluble copolymer was separated as Example 36 was repeated except that in this case 9 parts of phenyl glycidyl ether were copolymerized with 1 part of epichlorohydrin and the polymerization reaction was short-stopped after 1 hour at 30 C. by adding 4 parts of anhydrous ethanol. The ether-insoluble polymer was isolated as in the foregoing examples and amounted to 24% conversion. It was a white solid resembling crystalline poly (phenyl glycidyl ether) in appearance and had described in those examples and amounted to a 15% conversion. It was rubbery, had an RSV of 3.5 (0.1% solution in cyclohexanone at 50 C.), and by near infrared based on alkyl group analysis was shown to contain 6.7% of the allyl glycidyl ether monomer. The ether-soluble copolymer was recovered from the ether filtrates and washes by concentration of the ether solution and precipitation with methanol. After drying it was a viscous liquid and amounted to 11% conversion. The rubbery, etheran RSV of 2.8 (0.1% solution in a-chloronaphthalene at insoluble epichlorohydrin-allyl glycidyl ether copolymer was cross-linked by mixing on a two-roll mill 100 parts of the polymer with 12.5 parts of carbon black, 12.5 parts of neutral silica, 2 parts of sulfur, 5 parts of zinc oxide, 2 parts of stearic acid, and 2.5 parts of tetramethyl thiuram disulfide and then curing by heating at 310 F. for 40 minutes. The vulcanizate so obtained had a tensile strength of 2475 psi, :1 100, 200, 300 and 400% modulus of 315, 580, 935 and 1335 p.s.i., respectively, an ultimate elongation of 640%, break set of 15%, Shore hardness (A) of 61 and a tear strength of 205 lb./in.

EXAMPLE 39 Ten parts of cyclohexene oxide and 12 parts of diethyl ether were charged into an air-tree vessel, cooled to -78 C. and then 1 part of triisobutylaluminum which had been reacted with 0.1 mole of water per mole of aluminum in 5.6 parts of 50:50 ether:n-heptane was added. After 19 hours at 7S C., 4 parts of anhydrous ethanol and 35 parts of ether were added. The ether-insoluble poly(cyclohexene oxide) was collected, washed once with ether, once with a 1% solution of hydrogen chloride in ethanol and then with ethanol until neutral. It was finally washed with methanol containing 0.05% Santonox and was dried. This gave a 33% conversion of a tough, white, hard solid having an RSV of 1.00 (0.1% solution in chloroform at 25 C.). It was amorphous by X-ray. A portion of this polymer was compression molded for 3 minutes at 160 C. and 200 p.s.i. to give a very clear, glossy, hard film having a tensile strength of 4200 p.s.i., an ultimate elongation of 1.4% and a tensile modulus of 450,000 psi.

The ether-soluble poly(cyclohexene oxide) was obtained from the ether filtrates. The ether solution was washed twice with 3% aqueous hydrochloric acid, then with water until neutral, then with a 2% aqueous sodium bicarbonate solution, and finally was washed 3 times with water. It was then concentrated and the polymer was precipitated by adding an excess of methanol containing 0.05% Santonox. This ether-soluble, methanol-insoluble polymer was collected and dried to give a 10% conversion of a soft, white powder which was amorphous by Xray and had an RSV of 0.28 (0.1% solution in benzene at 25 EXAMPLE 40 Example 39 was repeated except that 10 parts of vinyl cyclohexene oxide was substituted for the cyclohexene oxide used in that example, and the polymerization was carried out at 30 C. for 19 hours. Only a trace of etherinsolu'ole polymer was obtained. The ether-soluble, methanol-insoluble polymer was isolated as described above and represented 84% conversion. This poly(vinyl cyclohexene oxide) had an RSV of 0.04 (0.1% solution in benzene at 25 C.) and was amorphous by Xray. It was a hard, somewhat brittle solid.

EXAMPLE 41 A mixture of 1.7 parts of ethyl glycidate and 3.1 parts of ether under a nitrogen atmosphere was cooled to 78 C. and 0.08 part of triethylaluminurn which had been prereacted with 0.6 mole of water per mole of aluminum in 08 part of diluent (58% ether and 32% n-heptane) was added. The polymerization reaction mixture was held at 78 C. for 17 hours, then at 40 C. for 22 hours, then at 18 C. for 33 hours and finally at C. for 44 hours after which 0.7 part of anhydrous ethanol was added. The polymer was precipitated by adding 40 parts of methanol and 1.6 parts of a solution of hydrogen chloride in methanol. The methanol-insoluble polymer was collected, washed neutral with methanol and then with methanol containing 0.7% Santonox and dried. The poly (ethyl glycidate) so obtained was a tough, somewhat rubbery, filmlil;e solid. It was largely insoluble in boiling benzene, but dissolved in boiling cyclohexanone and, after filtering and concentrating until viscous, it was recovered by heptane precipitation. The purified polymer was coli l lected, washed twice with ether and dried. It was a tough, white, somewhat rubbery solid which was of moderate crystallinity by X-ray. Its infrared spectrum was in accord with the assigned structure of poly(ethyl glycidate).

EXAMPLE 42 To a polymerization vessel with a nitrogen atmosphere atmosphere was charged 37.6 parts of diethyl ether, 15.3 parts of epichlorohydrin and 4.8 parts of propylene oxide. After equilibrating at 30 C., a catalyst solution was added in 4 equal portions at 30-minute intervals, said catalyst solution consisting of 1.58 parts of triisobutylaluminum complexed with 0.5 mole of Water per mole of aluminum in a 50:50 mixture of n-heptane and diethyl ether. After 20 hours at 30 C. the total conversion to polymer was 16%. The polymerization was stopped by adding 4 parts of anhydrous ethanol after which 35 parts of diethyl ether was added to the reaction mixture. It was then washed twice with a 3% aqueous solution of hydrogen chloride, then with water until neutral and then with a 2% aqueous solution of sodium bicarbonate. After again Washing with water, the ether-insoluble polymer was separated by centrifugation. This ether-insoluble polymer was washed with ether and then with ether containing 0.2% Santonox after which it was dried for 16 hours under vacuum. It was a white powder and crystalline by X-ray.

The ether-soluble polymer was recovered by combining the ether filtrate and washes, removing the ether until a viscous solution was obtained and then precipitating the polymer by adding about 10 volumes of methanol containing 0.2% Santonox. The methanol-insoluble polymer was then washed twice with the methanol Santonox solution and dried. This methanol-insoluble polymer amounted to a conversion of 2.7%, had an RSV of 1.0 and was a tacky rubber which was shown to be amorphous by X-ray. A chlorine analysis of this polymer showed that it contained 56% of the epichlorohydrin monomer.

EXAMPLE 43 To a polymerization vessel with a nitrogen atmosphere was charged 13.6 parts of diethyl ether, 6.7 parts of ethylene oxide and 3.3 parts of l,1-diethylarnino-2,3-epoxy propane. After equilibrating at 30 C. there was then injected 5.6 parts of a catalyst solution comprising a 50:50 mixture of diethyl ether and n-heptane and containing 0.79 part of triisobutylaluminum reacted with 0.5 mole of water per mole of aluminum, the catalyst solution being added in four portions at 30-minute intervals. After 19 hours at 30 C. the polymerization was stopped and the mixture was diluted with 35 parts of diethyl ether. The polymer was then isolated by centrifugation, washed once with ether and then with ether containing 0.2% Santonox. The polymer so obtained when dried Was a dark brown, catty-like solid. It was then extracted with hot toluene and the toluene-insoluble polymer was extracted twice with water. The water-soluble fraction was recovered by evaporating the water and drying. This water-soluble fraction amounted to an 8% conversion and was a brown, viscous liquid having an RSV of 0.07 in 0.1% solution in water at 25 C. A nitrogen analysis showed that this copolymer of ethylene oxide and 1,1- diethylamino-2,3-epoxy propane contained 28% of the amine monomer.

EXAMPLE 44 Ten parts of butadiene monoxide were polymerized by the same procedure as described in Examples 18 for epichlorohydrin. In this case the catalyst used was 046 part of triethylalurninum that had been reacted with 1 mole of acetylacetone per mole of aluminum for 20 hours at 30 C. and the diethylaluminum acetylacetonate so formed then reacted with 0.5 mole of water per mole of aluminum for 20 hours at 30 C. After 20 hours at 30 C. the polymerization was stopped by adding 4 parts of anhydrous ethanol, and the ether-insoluble polymer 15 was isolated and purified as described in those examples. The ether-soluble polymer was isolated from the ether filtrate and washes by precipitation with methanol. The data with respect to each of these polymers are tabulated 16 amount thereof expressed as parts of the alkylaluminum compound that was reacted with water in the indicated mole ratio, and reaction conditions (time and temperature) are tabulated in Table V along with the percent of below with the physical data on films prepared from each isolated polymer and RSV of each polymer as deterby compression molding for 5 minutes at 200 F. and mined on an 0.1% solution in chloroform at 25 C. for 300 p.s.i. poly(ethy-lene oxide) and an 0.1% solution in benzene at 25 C. for poly( propylene oxide). Ethan The ether-insoluble poly(ethylene oxide) produced in Et r- [Soluble Examples 45-51 was isolated by adding excess ether to Insoluble the reaction mixture, filtering and then washing with ether, then with 0.5% hydrogen chloride in an 80:20 Percent Conversion 18 mixture of ether:methanol, with ether:methanol alone RSV (11% in 9 at and then with ether containing 0.5% Santonox. The it???9 051511111113::1:113:: i; ill 15 polymer so obtained was a hard, v y tough, white solid. g g qi th 2 300 600 M. Pt. 66 C., which formed a very viscous 1% solution 52.35, fig gjj I: 68 290 in water. In Examples 45 and 49 there was also isolated Tensile modulus, D- 66,000 370 8% and 5%, respectively, of an ether-soluble, methanolinsoluble poly(ethylene oxide) that was a waxy, flaky An infrared spectrum on the ether-insoluble fraction solid. showed that polymerization took place through the oxide The poly(propylene oxide) produced in Examples 52 ring. The ether-soluble, methanol-insoluble fraction was and 53 was ether-soluble and was isolated by adding of low crystallinity but had the same infrared spectrum suflicient ether to make the solution of low viscosity for as the ether-insoluble fraction. ease in handling, then washing the reaction mixture first The ether-soluble, methanol-insoluble fraction was vulwith a 3% aqueous solution of hydrogen chloride, then canized by compounding on a two-roll mill 100 parts with water until neutral, then with a 2% aqueous soluof polymer, 50 parts of high abrasion furnace black, 2 tion of sodium bicarbonate and again with water. After parts of sulfur and 1.5 parts of mercaptobenzothiazole adding Santonox equal to 0.5% based on the polymer and then curing at 300 F. for 45 minutes. The vulto the reaction mixture, the ether was evaporated and the canizate so obtained had a tensile strength of 1695 p.s.i., 3Q polymer was dried. In each case it was a snappy rubultimate elongation of 245%, 100% and 200%, modulus ber. The product of Example 52 was further separated of 750 and 1250 p.s.i., respectively, and a Shore hardness into a crystalline and amorphous fraction by dissolving (A) of 73. the polymer in acetone at 65 C. at 1% concentration and The ether-soluble, methanol-insoluble fraction, which allowing it to crystallize for 16 hours at -18 C. The was also insoluble in n-heptane, was further fractionated crystalline polymer was collected, washed with acetone, by ether and found, after isolation, to be 68% insoluble then with acetone containing 0.05% Santonox, and dried. in ether. The latter ether-insoluble fraction was a tough, This crystalline fraction had an RSV of 10.2. The snappy rubber which was soluble in chloroform and had amorphous fraction, which was still a snappy rubber, had an RSV of 16.8. It had the same X-ray pattern as the an RSV of 5.7.

Table V Ex Diluent Reaction Isolated Polymer No. Monomer Catalyst Parts Conditions Total Components Percent RSV Parts Couv.

17. 6 84% ether, 16% n-heptaue..- E0 (i-C4H9)3Al-0.5HO 0. 79 10 Hrs., 30 C 32 1.05 46..." 17.6 do E0 (C211 )gAlAcetylacetonate-0.5H2O 0.74 19 Hrs.,30G 95 16.8 47 (i-onl xi-asrr drox aeetone-0.5H2o 0.79 191118., 40 o- 37 7.7 48-.. (CzH5 A105 (2,3-butane dione-2-oxime)- 0. 46 19 Hrs, 30 C 97 37 49.-. (871 1 3231025 oxalic acid-0.51120 0. 4e 19 Hrs, 30 0... 22 3. 0 50 (i-C4H )3A1-0.5 diethylma1onate-0.5HzO 0. 79 19 Hrs, 30 0... 50 5. 3 51 do (i-C4Hg)3Al-0.5 dimethyl glyoxime-0.5H;O 0. 79 19 Hrs, 30 C 89 18. 3 52 84% ether 16% n-heptaue.-- (C 115)zAlAcetylacetone-ojH o 0. 74 19 Hrs, 30 C 69 16. l 53 35 100% n-heptaue PO (i-C4H9)3A1-0.5Acety1acet0ne-0.5H2O 0.79 48 Hrs.,30 C 87 9.5

E0 =ethyle11e oxide; PO =propylene oxide.

first isolated ether-insoluble product but was only moderately high in crystallinity by X-ray. The ether-soluble fraction from this second fractionation was a snappy rubber having an RSV of 11.0 in chloroform and was of low crystallinity.

EXAMPLES 45-53 In these examples various alkylene oxides were polymerized using the general procedure described in Examples 1-8, using a mixture of ether and n-heptane or all n-heptane as diluent. The alkylaluminum compound that was prereacted with Water before using as the catalyst in Examples 46 and 52 was then chelate obtained by reacting triethylaluminum with an equimolar amount of acetylacetone and in Examples 47-51 and 53 was that obtained by reacting triethylaluminum or triisobutylaluminum with the indicated fraction of a mole of chelating agent per mole of aluminum prior to the reaction with the indicated mole ratio of Water. The monomer (10 parts in each case) polymerized, diluent, catalyst and EXAMPLES 54-74 In these examples various epoxides were copolymerized using the general procedure described in Examples 1-8. In each case the alkylaluminum compound was prereacted with the specified mole ratio of water as described in those examples. In Examples 65, 69 and 71 the catalyst solution was added in 2 equal portions 0.5 hour apart and in Example 60 the catalyst solution was added in 4 equal portions 0.5 hour apart.

In Table VI are set forth the monomers copolymerized and the amount of each, the diluent used and amount thereof, the catalyst and amount thereof expressed as parts of the alkylaluminum compound that was reacted with water or chelated with acetylacetone (A) and reacted with water in the indicated mole ratio, the reaction time and temperature and the percent conv. to isolated polymer obtained and the RSV of each polymer determined on an 0.1% solution in (1) chloroform at 25 C., (2) ot-chloronaphthalene at C., and (3) in benzene 17 at 25 C. The monomers copolymerized are indicated by the following abbreviations:

EO=ethylene oxide ECH=epichlorohydrin 18 The epichlorohydrin-ethylene oxide-allyl glycidyl ether of Example 61 was isolated by adding 1-2 volumes of 1% methanolic hydrogen chloride to precipitate the polymer, filtering, Washing the polymer first with methanol and EBl-lzgpibromohydyin then with an 0.2% solution of Santonox in methanol and PO=propylene oxide dfylllgt BMO=b t di id The ethylene oxide-propylene OXlde copolymer pro- VCMO=viny1cyc10he ene mgnoxide (1 2- 4 i 1. duced in Example 64 was isolated by addmg SllfilClfilll'. cyclohexane) acetone containing 2% water to give a handable but still AGEzallyl glycidyl ether viscous solution (cone. about 1%) and after centrifuging CEGE=2-chloroethyl glycidyl ethe to remove any insolubles, removing the diluents and dry- BCEO:1,l bis(chloromethynethylene oxide mg the polymer to constantweight. It was a rubbery, Mco:methallyl hl id id amorphous polymer soluble in ether and water, but was ECD:1,2 5,9- 1 d d i insoluble in n-heptane. Infrared analysis indicated that The copolymers obtained in Examples 54-56, 62, 63, the copolymer wmmed 41% propylene i 65 and 73 were isolated by adding 1-5 volumes of n-hep- The ethylene oxlde'pmPylene omde'butadlerte monox' tane to precipitate the polymer, filtering, and then washlde trpolymgr p m Example 74 3 Isolated as ing with n-heptane and a 0.2% solution of Santonox in descnbed for the i of the i i m Examplc mhEPtane and finally drying for 16 hours at 00 C. in It had the same solubility characteristics as the ethylene lama 20 oxide-propylene oxide copolymer of Example 64 and rep- The copolymers Obtained in Examples 57 and 6641 resents a unique water-soluble sulfur vulcanizable elaswere isolated in the same manner as described for Examf Infrared analysls f that the Polymer ples 52-53. A similar procedure was used for isolating talnfid about 6% ethylene oxide, 42% propylene mode the propylene oxide-l,2-epoxy-5,9-cyc1ododecadiene coand 12% butadlene monoxlde; polymer of Example 72 except that the polymer was The copolymers produced 111 these mp were all washed 3 times with 10% sodium hydroxide and then g y amorphous, a number of them e completely with water until neutral instead of with acid, etc. amorphous as Shown by Y diffraction- T able VI Dlluent Isolated Polymer Ex. Reaction No. Monomer Parts Catalyst Parts Conditions Total Components Percent RSV Parts Conv.

54 2% (C2Hs)aAl-0.5A-O.5H2O 0.23 6Hrs.,30 0---- 22 11.4 (1) 55"--. 40 s it (CzH5)sAl-O.5A-0.5H2O 0.23 27 Hrs.,30 o--- 19 9.2 (2) 5am do 1 (CeH Al-0.5A-0.5H2O 0.23 30 Hrs.,3() o- 21 9.0 2) 57.--" 31 13 (cinenAi-osn-osneo- 0.23 19 Hrs, 30 0... 28 14.5 (3) 5s 20 (C2H5)2A1A-0.5H20 0.45 4Hrs.,50 0---. 7 6.7 2

59 20 (Queenie-0.51320 0.45 4Hrs.,50C 6.5 1.1 2 60..- 44 1g (l-C4Hs)3Al-0-5H20------ 1.58 5.5 Hrs.,30 o 74 2.1 2 61 to s (oinenaroda-osrrrofi- 0.23 27Hrs.,30 0-.-- 12 5.4 2

1 62"- 40 (C2H Al-O.5A-G.5H20 0.23 27 Hrs.,30 o 9 112 (3) 39 (CrH Al-0.5A-0.5HzO 0.23 4Hrs.,30 c 16 11.7 (1

it e4 17.6 84% ether, 16% rrhe tene.-. g' (c2Hslfl -5H2 0.74 6Hrs.,30 o 11.9 1 65"-.- 28.6 n-Heptane 22; (CzHs)zAlA-0.5 z0 0.46 5131's., 30 C 18 14.6(1) 66 t7. 6 84% ether, 16% n-lleptane... i ll 5)2 2O 0. 74 8 Hrs.,30O 22 9. 8 (3) 67 66 n-Heptane 1? (C2H5)aA -0-5 -0.5H2O 0.23 7Hrs.,50 C 21 15.8 (3) 68 17. 6 20% ether, 80% n-Heptaue-.. (C2Hs)2A1A-0.5H2O 0.74 4 Hrs, 30 C 11 12.5 (3) 69 2 5 (C2H5)3Al-0.5A-U.5H20 0.46 7.5 Hrs.,30 o--- 41 92(3) 70 g (C2H5)aAI-U.5A-(L5H2O 0.45 5 Hrs, 30 C 27 6.7 (3) 71 40 Toluene PO (C2H5)3A1'0-5A'0-5H20 0. 45 (Hits, 30 O 13 12.7 (3) 72 29 n-Heptane... g (C2H5)2AlA-0.5H2O 0.45 4Hrs.,30 C 16 7.8(3) 73 4O Toluene (C2 s)a 1-0 5A-0.5Hz0 0.23 22 Hrs.,30 C-.. 19 8.7(3)

.0 1.0 74..- 17.6 84% ether, 16% n-Heptane... (C2H5)2A1A-045H20 0.74 6Hrs.,30 (3..-- 31 23.0 (1) BM'dILII 1' See explanation of abbreviations and notes under Examples 54-74, col. 17.

A description of the copolymers produced in Examples 70 54-74 is summarized in Table VII along with the physical data on vulcanizates prepared from a number of them. The vulcanization was done by compounding on a tworoll mill (roll temperature of 175 F.) for 5-7 minutes, parts of the polymer with the specified vulcanization formula and then press curing at 310 F. for 40 minutes.

ether several times. In Example 75 a 57% conversion to a powdery solid which was insoluble in a-chloronaphthalene at the boiling point was obtained. In Example 76 See explanation of abbreviations under Examples 54-74, 001. 17.

EXAMPLES 75 AND 76 The diglycidyl ether of bisphenol A, i.e. 2,2-(4-hydroxyphenyDpropane, was homopolymerized and copolymerized with butene-l epoxide following the same general procedure used in the foregoing examples, except that no diluent, other than that present in the catalyst solution was used. In Example 75 the polymerization vessel was charged with 10 parts of the diglycidyl ether of bisphenol A and the catalyst added was 0.79 part of triisobutylaluminum which had been reacted with 0.5 mole of water per mole of aluminum. In Example 76 the polymerization vessel was charged with 5 parts of the diglycidyl ether of bisphenol A and 5 parts of butene-l epoxide and the catalyst added was 0.46 part of triethylaluminum reacted with 0.5 mole of acetylacetone per mole of aluminum and the chelate then reacted with 0.5 mole of water per mole of aluminum. After 21 hours at 30 C. the polymers were isolated by washing the reaction mixture, which was a solid white mass in each case, with Formula N I 11 111 there was obtained a 41% conversion to a tough, rubbery copolymer which was also insoluble in a-chloronaphtha- Fast extruding furnace black 30 lene at the boiling point. 2 558 i As may be seen from the foregoing examples, the proc- Stearie AeiEi.' I: 2 ess of this invention makes it possible to produce a wide 4 variety of polymeric epoxides and obtain higher conver- Mercaptobenzothiazole -1: 1.5 sions or other improved results. Thus, in some cases it is possible to produce extremely high molecular weight The copolymers of Examples 66 and 74 were vulcanized P y and p ym W111ch 1H cases have not by a f l like that f 1 but using 50 Parts f l k heretofore been available and these higher molecular instead of 30 (designated as Ia) and the copolymer of welght p y have much greater utlhty a the P Example 68 was vulcanized by the Formula I except art p y In other cases 1t has been posslble to p that no black was used (designated as Ib). The trip crystalhne p y from monomers that have P ethylenediamine used above was 1,4diazobicyclo(2.2.2) VIOUSIY bflen Polymeflled y to VISCOUS 011$ to 10W octane, molecular weight amorphous materlals.

Typical of the advantages to be found in many of these h polymeric eP0XIdes P 111 afiicofdallce Wlth copolymers i th l i t f h propylene id this invention may be used for a wide variety of applicaa-llyl glycidyl ether (Example 67) which in addition to trons. Many of these polymers are rubber-like in nature the excellent properties shown in Table VII, is also found and hence y be used as lube Oil additives, Wax addito be superior to natural and GR-S rubbers in its hysteretives, caulking compounds, adhesive components, etc., and sis properties (lower heat build-up on flexing) and in its when vulcanized as compositions for gaskets, hoses and low temperature properties. rubber compositions in general. Others are crystalline Table VII Acetone Ulti- Shore Percent Ex. Copolymer Composr- Water Solu- Vulcan- Tensile Modulus mate Hard- Gel Percent N0. tion, Percent by Description Solubility, ization Strength, 300%, Elonganess Forma- Swell Weight bility Percent Formula p.s.i. p.s.i. tion, A2 tion (Toluene) Percent 54... 156111150, 14:86 Hard, tough 100 TT 93 740 rubber. Snappy rubber" 83 II 1, 325 1, 140 330 100 180 Tough rubber-..

II 310 160 650 37 99 185 111 72 600 do Insol II 970 s5 100 59 34 7 Snappy rubber Ins0l I 1, 710 250 64 100 02... ngr'r e rgnaon, do Ins0l- 70 I 2,710 1,140 530 59 99 280 Tough rubber 86%-.- 100 I 3, 090 1,800 540 78 98 230 Rubber S Tough rubber". Larglely 0 66 P0;BMO, s0;20 Snappy rubber Ius01 Ia 1,690 1, 340 410 81 67.-. PO:AGE,92:8 Tough snappy Inso1 I 2,190 820 625 55 97 405 I11 er. 68 PO:VCMO,99:1 d0 Ins01 Ib 86 1,920 69-" PO:OEGE,78:22 Tough rubber Inso1 1,130 1, 080 310 56 94 295 70.. POzBCEO, 99.3:0 7 Snappy rubber 71--- PO:MCO,99:1 Rubber I 72 PO:ECD,91:9 Snappy rubber-. 73--- Pg igg AGE, 1,250 605 490 60 97 395 74.-. roi'noiiaivro, 1, 515 1, 310 400 81 and are useful as plastics, as film-formers, in coatings, for fibers, etc.

What I claim and desire to protect by Letters Patent is:

1. As a new composition of matter, a polymerization catalyst consisting of the organoaluminum oxide formed by reacting an organoaluminum compound free of ethylenic unsaturation with water in an amount such that the molar ratio of water to organoaluminum compound is within the range of from about 0.1 to about 1.5 and such that said organoaluminum oxide retains at least some of the aluminum-to-carbon bonds present in the organoaluminum compound so reacted.

2. The composition of claim 1 wherein the organoaluminum compound reacted is selected from the group consisting of trialkylaluminum, dialkylalurninum hydride and alkylaluminum halides.

3. As a new composition of matter, a polymerization catalyst consisting of the organoaluminum oxide formed by reacting a trialkylaluminum with water; in an amount such that (l) the molar ratio of water to the trialkylaluminum is within the range of from about 0.1 to about 1.5 and (2) there remains in the reaction product at least about one aluminum-to-carbon bond per mole of aluminum.

4. As a new composition of matter, a polymerization catalyst consisting of the organoaluminum oxide formed by reacting a dialkylaluminum hydride with water in an amount such that (1) the molar ratio of water to the dialkylaluminum hydride is within the range of from about 0.1 to about 1.5 and (2) there remains in the reaction product at least about one aluminum-to-carbon bond per mole of aluminum.

5. As a new composition of matter, a polymerization catalyst comprising the organoaluminum oxide formed by reacting an organoaluminum compound free of ethylenic unsaturation with from about 0.01 to about 1.5 moles of a chelating agent per mole of aluminum compound, and with from about 0.1 to about 1.5 moles of water per aluminum compound, the total amount of said chelating agent and water reacted with said organoaluminum compound being such that said organoaluminum oxide retains at least some of the aluminum-to-carbon bonds present in the organoaluminum compound so reacted, said chelating agent being an organic compound having two functional groups, one of which is selected from the group consisting of OH and SH, and the other is a group containing an element selected from the group consisting of O, N, and S, which forms a co-or-dinate bond with aluminum.

6. The product of claim 5 wherein the organoaluminum compound is a trialkylaluminum.

7. The product of claim 6 wherein the chelating agent is acetylacetone.

8. The product of claim 2 wherein the molar ratio of Water to organoaluminum compound is within the range of from about 0.2 to about 1.

9. As a new composition of matter, a polymerization catalyst comprising the organoaluminum oxide formed by reacting a trialkylaluminum with about 0.5 mole of acetylacetone per mole of aluminum and with about 0.5 mole of water per mole of aluminum.

10. As a neW composition of matter, a polymerization catalyst comprising the organoaluminum oxide formed by reacting a trialkylaluminum in the presence of an ether with about 0.5 mole of acetylacetone per mole of aluminum and with about 0.5 mole of water per mole of aluminum.

References Cited by the Examiner UNITED STATES PATENTS 2,699,457 1/1955 Ziegler et al 260448 2,801,228 7/1957 Schlenkcr et al. 1.. 2602 2,866,761 12/1958 Hill et al 2602 2,870,100 1/1959 Stewart et a1. 260-47 2,984,658 5/ 1961 Seydel et al 260-94.9

OTHER REFERENCES Ziegler: Uspekhi Khimii, Vol. 26, 1957, pp. 1187-1200 (page 1198 relied on).

Calcough ct al.: J. Polymer Science, Vol. 34, page 179, January 1959.

TOBIAS E. LEVOW, Primary Examiner. 

1. AS A NEW COMPOSITION OF MATTER, A POLYMERIZATION CATALYST CONSISTING OF THE ORGANOLUMINUM OSIDE FORMED BY REACTING AN ORGANOALUMINUM COMPOUND FRE OF ETHYLENIC UNSATURATION WITH WATER IN AN AMOUNT SUCH THAT THE MOLAR RATIO OF WATER TO ORGANOALUMINUM COMPOUND IS WITHIN THE RANGE OF FROM ABOUT 0.1 TO ABOUT 1.5 AND SUCH THAT SAID ORGANOALUMINUM OXIDE RETAINS AT LEAST SOME OF THE ALUMINUM-TO-CARBON BONDS PESENT IN THE ORGANOALUMINUM COMPOUND SO REACTED. 